Rhodium-Catalyzed Tandem Reaction of <i>N</i>-(Pivaloyloxy)acrylamides with 1,3-Diynes for the Synthesis of Furo[2,3-<i>b</i>]pyridines

We disclose a rhodium-catalyzed tandem reaction of <i>N</i>-(pivaloyloxy)acrylamides with 1,3-diynes for the efficient synthesis of furo[2,3-<i>b</i>]pyridines. This unique tandem reaction includes C-H activation, Lossen rearrangement, [4+2] annulation, and [3+2] annulation in "one pot", which features readily available substrates, broad functional group compatibility, and the ability to isolate pure products through simple filtration under ambient conditions with excellent regioselectivity, selectivity for mono- or diannulation, and intra- and intermolecular annulation selectivity. Furthermore, this synthetic protocol facilitates the rapid construction of a diverse library of blue-emitting molecules with high quantum yields, providing a valuable platform for developing advanced functional materials.